Certain 2-benzoxazolinone and 2-benzothiazolinone derivatives of 0,0-dialkyl s-(2-haloethyl) phosphorothioates and dithioates

ABSTRACT

Disclosed are compounds of the formula:   WHEREIN EACH R is a lower alkyl radical, Y is selected from the group consisting of the oxo and thioxo radicals, X is a halo radical, A is selected from the group consisting of the oxy and thio radicals, and each R&#39;&#39; is selected from the group consisting of the hydrogen and halo radicals. These compounds are highly toxic to southern army worm larvae.

D United States Patent 51 3,668,213 Jamison 1 June 6, 1972 [54] ANDPrimary Examiner-Alex Maze! 2.BENZ()THIAZOLINONE Assistant ExaminerR. J.Gallagher DERIVATIVES OF 0,0-DIALKYL sz- HPPmS HALOETHYL)PHOSPHOROTHIOATES ABSTRACT AND DITHIOATES Disclosed are compounds of theformula: [72] Inventor: Joel D. Jamison, New Castle, Del.

R! [73] Assignee: Hercules Incorporated, Wilmington, Del. 22 Filed: May20, 1970 0:0 21 App]. No.. 51,032 R \N/ Related u.s. Application nm [63]Division of Ser. No. 801,767, Feb. 24, 1969, Pat. H Y O-R No. 3,529,059,which is continuation-in-part of Ser. No. 601,553, Dec. 14, 1966,abandoned, which is a l I continuation-in-part of Ser. No. 535,735, Mar.21, El 1966, Pat. No. 3,355,353, which is a continuationwherein each Ris a lower alkyl radical, Y is selected from the in-part of SerNo.417,516, De 10, 1964, abandoned, group consisting of the 0x0 and thioxoradicals, X is a halo radical, A is selected from the group consistingof the oxy and 52 US. Cl. "260/304, 260/307 0 thio radicals, and each isSelected from the group consisting [5|] ll'lt-Cl. t ..C07d 91/24 of thehydrogen and halo radicals These compounds are [58] Field of Searchhighly toxic to southern army worm larvae.

23 Claims, No Drawings CERTAIN Z-BENZOXAZOLINONE AND 2-BENZOTHIAZOLINONE DERIVATIVES F 0,0-DIALKYL S-(Z-HALOETHYL)PHOSPI-IOROTHIOATES AND DITHIOATES The application is a divison of theapplication, Serial No. 801,767, filed Feb. 24, 1969, on which Patent3,529,059 was granted, which itself was a continuation-in-part of theapplication, Ser. No. 601,553, filed Dec. 14, 1966, now abandoned whichis a continuation-in-part of the application Ser. No. 535,735, filedMar. 21, 1966, on which US. Pat. No. 3,355,353 was granted and which inturn is a continuation-inpart of the now abandoned application, Ser. No.417,516, filed Dec. 10, 1964.

This invention is in the chemical arts. It relates to that part oforganic chemistry having to do with organo sulfurphosphorous compounds,and to insecticidal compositions containing organo sulfur-phosphorouscompounds.

This invention comprises certain novel phosphorothioates andphosphorodithioates, and novel insecticidal compositions containingthem.

The phosphorothioates and phosphorodithioates of this invention arerepresented by the general structural formula I:

wherein each R is a lower alkyl radical, Y is selected from the groupconsisting of the 0x0 and thioxo radicals, X is a halo radical, A isselected from the group consisting of the oxy and thio radicals, andeach R' is selected from the group consisting of the hydrogen and haloradicals. The R radicals can be the same or different. A lower alkylradical is an alkyl radical having one-seven carbon atoms, and can beeither straight or branched. Examples of a lower alkyl radical includethe methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc.radicals. The halo radicals in those compounds having more than one haloradical can be the same or different. Examples of the halo radical arethe fluoro, chloro, bromo and iodo radicals. Examples of the compoundsof this invention include:

0,0-dimethyl S- [2-chloro-l-(2-benzoxazolinone-3'-yl)- ethyl]phosphorodithioate 0,0-dimethyl S-[2-bromo-l-(2'-benzoxazolinone-3'-yl)- ethyl] phosphorodithioate0,0-dimethyl S- [2-fiuoro-l-(2'-benzoxazolinone-3'- yl)ethyl]phosphorodithioate 0,0-dimethyl S- [2-iodo-l-(2'-benzoxazolinone-3'-yl)-ethyl] phosphorodithioate 0,0-diethyl S-[2-chloro-l-(2'-ben2oxazolinone-3'-yl)- ethyl] phosphorodithioate0,0-diethyl S- [2-brom0-l-(2'-benzoxazolinone-3'-yl)- ethyl]phosphorodithioate O-methyl-O-ethyl S- [2-chlorol 2 '-benzoxazolinone-3yl)ethyl] phosphorodithioate 0,0-dipropyl S-[2-chloro-1-(2'-benzoxazolinone-3'-yl)- ethyl] phosphorodithioate0,0-diisopropyl S- [2-chloro-1-(2 '-benzoxazolinone-3yl)ethyl]-phosphorodithioate Y 0,0-diheptyl S-[2-chloro-1-(2'-bcnzoxazolinone-3-yl)- ethyl] phosphorodithioate0,0-diethyl S- [2-chloro-l-(6'-chloro-2-benzoxazolinone- 3-yl)ethyl]phosphorodithioate azolinone-3 '-yl )ethyl] phosphorodithioate0,0-diethyl S- [2-chloro-l-(5', 6-dichloro-2'-benzoxazolinone-3-yl)ethyl] phosphorodithioate 0,0-diethyl S- [2-iodol',6-dichloro-2-benzoxazolinone-3-yl)ethyl] phosphorodithioate0,0-diethyl S- [2-chloro-l-(2'-benzoxazolinone-3-yl)- ethyl]phosphorothioate 0,0-diethyl S-[2-chloro-l-(6-chloro-2'-benzoxazolinone- 3-yl)ethyl] phosphorothioate0,0-diethyl S- [2-fluoro-l-(6-chloro-2-benzoxazolinone- 3'-yl)ethyl]phosphorothioate 0,0-dimethyl S- [2-bromo-1-(2'-benzothiazolinone-3-yl)ethyl] phosphorodithioate 0,0-dimethyl S-[2-chloro-l-(2-benzothiazolinone-3'- yl )ethyl] phosphorodithioate0,0-dimethyl S- [2-iodol 2 -benzothiazolinone-3 '-yl ethyl]phosphorodithioate 0,0-dimethyl S- [2-fluoro-l-(2'-benzothiazolinone-3-yl )ethyl] phosphorodithioate 0,0-diethyl S-[2-bromo-l-(2-benzothiazolinone-3'-yl)- ethyl] phosphorodithioate0,0-diethyl S- [2-chlorol 2 '-benzothiazolinone-3 yl )ethyl]phosphorodithioate O-methyl-O-ethyl S-[ 2-bromol 2 '-benzothiazolinone-3yl)ethyl] phosphorodithioate 0,0-dibutylS-[2-bromo-l-(2'-benzothiazolinone-3'- yl)ethyl] phosphorodithioate0,0-diisobutyl S-[ 2-bromol 2'-benzothiazolinone-3 yl)ethyl]phosphorodithioate 0,0-di-t-buty1 S-[ 2-bromol 2 -benzothiazolinone-3yl)ethyl] phosphorodithioate 0,0-dihexyl S-[ 2-bromol 2'-benzothiazolinone-3 yl)ethyl] phosphorodithioate 0,0-diethylS-[2-iodol-( 6-chloro-2-benzothiazoli-none- 3 '-yl )ethyl]phosphorodithioate 0,0-diethyl S[ 2-chlorol 2 '-benzothiazolinone-3yl)ethyl] phosphorothioate O-methyl-O-propyl S- 2-fluorol 4 '-bromo-2-benzothiazolinone-S '-yl)ethyl] phosphorothioate In generalthecompounds of this invention at 20-25 C. are oils that are highlyinsoluble in water, but soluble in solvents such as acetone and theline, and benzene and the like. In general they are biologically active,being toxic to a number of insects such as, for example, Mexican beanbeetle, pea aphid, mosquito larvae and particularly southern army wormlarvae. Consequently, the compounds of this invention are useful asinsecticides and especially as southern army worm toxicants.

Each compound of this invention is made by reacting a compound of thegeneral structural formula ll:

wherein each X and each R are defined in the case of structural formulaI, with a compound of the general structural formula III:

wherein each R and Y are defined in formula I, and M is a cationicradical, examples of which include the ionic hydrogen, ammonium, amino,pyridinium, alkali metal (sodium, potassium and the like), and the likeradicals. When M is the ionic hydrogen radical, reaction is preferablyeffected with the aid of a metal, such as, for example, finely dividedzinc or the like, a metallic salt, such as, for example, zinc chlorideor the like. Preferably the reaction is carried out at atmosphericpressure and 20-l00 C. in a normally liquid reaction medium in which theorganic reactant is soluble. Examples of a normally liquid reactionmedium include acetonitrile, normal liquid ketones (acetone, methylethyl ketone), water, dimethylformamide, dimethyl sulfoxide and ethylacetate. When the pyridinium or trialkyl ammonium salts are used,aromatic solvents such as benzene and toluene, are preferred.

For use as insecticides and particularly as southern army wormtoxicants, the compounds of this invention are preferably embodied intodispersible compositions. Such a composition generally comprises adispersible carrier. Specific embodiments of these dispersiblecompositions include dispersible solid compositions and dispersibleliquid compositrons.

In the case of a dispersible solid composition, the carrier generally isa dispersible inert solid, examples of which are well known in theinsecticide art. A typical dispersible solid of this type is clay. Othersuitable solid dispersible solids include talc, attapulgite,pyrophylite, diatomaceous earth, kaolin, aluminum and magnesiumsilicate, montmorillonite, fullers earth, corn cobs, saw dust, and thelike. The solid dispersible composition can be air dispersible, in whichcase it can be applied as a dust. It can be water dispersible, andgenerally when it is intended that the composition be water dispersible,the composition preferably contains emulsifying material (one or moresurfactants) at a concentration sufiicient to enable a suspension of thedesired degree of stability to be formed when the composition is admixedwith a suitable quantity of water. A typical dispersible solidcomposition of this invention generally comprises 10-50 percent byweight of active or toxicant material. The toxicant material comprisesat least one compound of this invention. In some embodiments itcomprises more than one compound of this invention. In other specificembodiments it comprises not only one or more compounds of thisinvention, but other toxicants such as for example, toxaphene,parathion, methyl parathion, and the like. A dispersible liquidcomposition generally comprises dispersed in water a solution oftoxicant or active material in an inert, volatile, water immisciblesolvent for the toxicant material. The solution or concentrate typicallycomprises l50 percent by weight of toxicant material and 50-90 percentby weight of solvent. Preferably the composition also comprisesemulsifying material at a concentration sufficient to enable adispersion of the desired degree of stability to be formed. A typicalemulsifying material concentration is 1-10 percent by weight of theconcentrate. The water concentration is such that the toxicant materialconcentration is about 0.5- percent by weight of the total composition.

Examples of the surfactants employed in both the liquid and soliddispersible compositions of this invention comprise the well-knownsurface active agents of the anionic, cationic or non-ionic types andinclude alkali metal (sodium or potassium) oleates and similar soaps,amine slats of long chain fatty acids (oleates), sulfonated animal andvegetable oils (fish oils and castor oil), sulfonated petroleum oils,sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids,alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodiummonolaurylphosphates, sorbitol laurate, pentaerythritol monostearate,glycerol monostearate, polyethylene oxides, ethylene oxide condensatesof stearic acid, stearyl alcohol, stearyl amine, rosin amines,dehydroabietyl amine and the like, lauryl amine salts, dehydroabietylamine salts, lauryl pyridinium bromide, stearyl trimethylammoniumbromide, and cetyl dimethylbenzylammonium chloride.

The dispersible compositions of this invention are made by conventionalways and means well known in the art.

The dispersible compositions of this invention are used by applying themby conventional ways and means to the habitat of the insects to bekilled or to the plants to be protected. Generally, they are applied atrates of one-fourth-lO pounds of active or toxic material per acre.Higher and lower effective rates, however, are within the broaderconcepts of this inventron.

The best mode now contemplated for carrying out this invention isillustrated by the following working examples of various aspects of theinvention, including specific embodiments. This invention is not limitedto these specific embodiments. In these examples, all percentages are byweight unless otherwise indicated, all parts by weight are indicated by"w", all parts by volume are indicated by v, and each part by weight (w)bears the same relationship to each part by volume v as the kilogramdoes to the liter.

EXAMPLE 1 This example demonstrates the preparation of 0,0- dimethyl S-[2-chlorol 2'-benzoxazolinone-3 '-yl)ethy1] phosphorodithioate.

A mixture of 7.0 w of 3-( l ,2-dichloroethyl)-2-benzoxazolinone and 5.3w of ammonium 0,0-dimethyl phosphorodithioate in 50 v of acetonitrile isallowed to stand at 20-25 C. for 18 hours and then at 50 C. for 2 hours.The reaction mixture thus formed is filtered, concentrated, diluted withbenzene and the benzene solution washed with 5 percent sodiumbicarbonate and water. After drying the benzene solution over magnesiumsulfate, the benzene is removed to give an oil. A typical yield of theoil is 7.4 w. This oil consists essentially of 0,0-dimethyl S-[2-chlorol 2benzoxazolinone-3 -yl)ethyl] phosphorodithioate. A typicalanalysis of the oil gives 8.8 percent phosphorous. The calculatedphosphorous content of the compound is 8.9 percent.

EXAMPLE 2 This example illustrates how to make 0,0-dimethyl S-[2- bromol2'-benzoxazolinone-3 '-yl )ethyl] phosphorodithioate.

A mixture of 16.1 w 3-( l,2-dibromoethyl)-2-benzoxazolinone and 9.6 w ofammonium 0,0-dimethyl phosphorodithioate in v of acetonitrile is stirredat about 25 C. for 18 hours and then at 60 C. for 4 hours. The mixtureis cooled, poured into 1,000 v of water, and extracted with benzene. Thebenzene solution is washed first with 5 percent aqueous sodiumbicarbonate and then with water, and dried. The benzene is removed togive the desired product. It typically is an oil consisting essentiallyof 0,0-dimethyl S-[2- chloro-l-(2'-benzoxazlolinone-3'-yl)ethyl]phosphorodithioate. A typical yield of the product is 14.7 w. A typicalanalysis of the product indicates 7.8 percent phosphorous. Thecalculated phosphorous content of the compound is 7.9 percent.

EXAMPLE 3 In this example, 0,0-diethylS-[2-chloro-l-(2'-benzoxazolinone-3 -yl )ethyl] phosphorodithioate ismade.

Following the procedure of Example 2, 108.2 w of 3-( 1,2-dichloroethyl)-2-benzoxazolinone and 110.0 w of ammonium 0,0-diethylphosphorodithioate are reacted in 500 v of acetonitrile and a product isisolated. A typical yield is 179.6 w. It typically is a solid consistingessentially of 0,0-diethyl S- [2-bromol-( 2-benzoxazolinone-3 -yl)ethyl] phosphorodithioate. A typical phosphorous content of the productis 8.5 percent. The calculated phosphorous content of the compound is8.1 percent.

EXAMPLE 4 This example shows how to make 0,0-diethyl S-[ 2-bromo-l-(2-benzoxazolinone-3-yl)ethyl] phosphorodithioate.

By the procedure of Example 2, 16.1 w of 3-( 1,2-dibromoethyl-2-benzoxazolinone, and 11.2 w of ammonium 0,0-diethylphosphorodithioate are reacted in 100 v of acetonitrile and a product isseparated from the reaction mixture. It typically is an 011 (20.4 w)which consists essentially of 0,0-diethylS-[Z-bromo-1-(2-benzoxazolinone-3-yl)ethyl] phosphorodithioate. Theproduct typically analyzes 7.8 percent phosphorous. The calculatedphosphorous content of the compound is 7.3 percent.

EXAMPLE 5 This example relates to 0,0-diethyl S-[2-chloro-l-(6- chloro-2'-benzoxazolinone-3 '-yl )-ethyl phosphorodithioate and its production.

By the procedure of Example 2, 13.4 w of 6-chloro-3-(l,2-dichloroethyl)-2-benzoxazolinone and 12.0 w of ammonium 0,0-diethylphosphorodithioate are reacted in 100 v of acetonitrile and the desiredproduct isolated. It typically is an oil (18.1 w) which consistsessentially of 0,0-diethyl S-[2- chlorol6'-chloro-2'-benzoxazolinone-3'-yl )ethyl] phosphorodithioate. A typicalanalysis of the product indicates 7.5 percent phosphorous (thecalculated value for phosphorous in the compound is 7.4 percent).

EXAMPLE 6 This example demonstrates how to make 0,0-diethyl S-[2-chloro- 1-( 5 ,6'-dichloro-2'-benzoxazolinone-3'-yl)ethyl]phosphorodithioate.

By the procedure of Example 2, 11.0 w of3-(l,2-dichloroethyl)-5,6-dichloro-2-benzoxazolinone, and 8.3 w ofammonium 0,0-diethyl phosphorodithioate are reacted in 100 vacetonitrile, and the desired product is isolated. The product typicallyis an oil. It consists essentially of 0,0-diethyl S-[2-chloro--(5 ,6-dichloro-2 -benzoxazolinone-3 yl)ethyl] phosphorodithioate. Typicallyit analyzes 5.3 percent phosphorous (the calculated phosphorous contentof the compound is 6.8 percent).

EXAMPLE 7 This example illustrates the making of 0,0-diethyl S-[2-chlorol -(2-benzoxazolinone-3'-yl)ethyl] phosphorothioate.

Following the procedure of Example 2, 11.6 w of 3-(1,2-dichloroethyl)-2-benzoxazolinone and l0.3 w of ammonium 0,0-diethylphosphorothioate are reacted in 100 v of acetonitrile and a productconsisting essentially of 0,0-diethyl S-[ Z-chlorol 2 -benzoxazolinone-3-yl)ethyl] phosphorothioate is isolated. The product typically is an oil(16.9 w) and analyzes 8.6 percent phosphorous (the calculated value forphosphorous in the compound is 8.5 percent.

EXAMPLE 8 In this example 0,0-diethyl S-{2-chloro-1-(6'-chloro-2-benzoxazolinone-3 -yl)ethyl] phosphorothioate is made.

Using the procedure of Example 2, 9.3 w of 6-chloro-3-( 1,2 ishlwqst xl- -bsnz xaz inqn and-J w of ammonium 0,0-diethyl phosphorothioate arereacted in 100 v of acetonitrile and the desired product is isolated. Ittypically is an oil 12.4 w) which consists essentially of 0,0-diethylS-[2- chloro- 1-( 6'-chloro-2-benzoxazolinone-3-yl)ethyl]phosphorothioate, and analyzes 7.7 percent phosphorous (the calculatedphosphorous content of the compound is 7.8 percent.

EXAMPLE 9' Here, 0,0-dimethyl S-[2-bromo-l-(2-benzothiazolinone-3'-yl)ethyl] phosphorodithioate is made.

A mixture of 12.0 w of 3-( l,2-dibromoethy1)-2- benzothiazolinone and6.8 w of ammonium 0,0-dimethyl phosphorodithioate in 100 v ofacetonitrile is stirred 18 hours at 25 and 4 hours at 60. The mixture ispoured into water, the resulting oil taken into benzene, the benzenesolution washed first with 5 percent aqueous sodium bicarbonate and thenwith water, and dried over anhydrous magnesium sulfate. The benzene isremoved to give a product consisting essentially of 0,0-dimethylS-[Z-bromol 2'-benzothiazo-linone-3 '-yl)ethyl] phosphorodithioate. Theproduct typically is an oil (12.6 w) analyzing 7.1 percent phosphorous(the calculated phosphorous content of the compound is 7.7 percent).

EXAMPLE 10 In this example 0,0-dimethylS-[2-chloro-l-(2'-benzothiazolinone-3'-yl)ethyl] phosphorodithioate isproduced.

By the procedure of Example 9, 14.9 w of 3-( 1,2-dichloroethyl)-2-benzothiazolinone and 11.6 w of ammonium 0,0-dimethylphosphorodithioate are reacted in 100 v of acetonitrile and the desiredproduct consisting essentially of 0,0-dimethyl S-[ 2-chlorol2'-benzothiazolinone-3 yl)ethyl] phosphorodithioate is isolated. Thisproduct is typically an oil (18.0 w), which analyzes 7.9 percentphosphorous and 9.8 percent chlorine. The calculated phosphorous andchlorine values for the compound are 8.6 percent and 9.7 percentrespectively.

EXAMPLE 1 l 0,0-Diethyl S-[2-bromo-l-2'-benzothiazolinone-3'- yl)ethyl]phosphorodithioate is the compound made in this example.

The procedure of Example 9 is followed to react in acetonitrile (100 v)3'-( l,Z-dibromoethyl)-2-benzothiazoline 12.0 w) and ammonium0,0-diethyl phosphorodithioate (8.0 w), and to isolate a productconsisting essentially of 0,0- diethylS-[2-bromo-l-(2-benzothiazolinone-3-yl)ethyl] phosphorodithioate. Theproduct (15.4 w) is typically an oil, which analyzes 7.3 percentphosphorous (the theoretical phosphorous value for the compound is 7.2percent).

EXAMPLE 12 This example shows how to make 0,0-diethyl S-[2-chloro-l 2'-benzothiazolinone-3 '-yl )ethyl] phosphorodithioate.

The procedure of Example 9 is followed to react 14.9 w of 3-(1,2-dichloroethyl)-2-benzothiazolinone and 13.4 w of ammonium0,0-diethyl phosphorodithioate in 100 v of acetonitrile, and to isolatea product consisting essentially of 0,0-diethyl S-[Z-chlorol2'-benzothiazolinone-3 -yl )ethyl] phosphorodi-thioate. The producttypically is an oil (21.3 w) analyzing 7.4 percent phosphorous (thetheoretical phosphorous content of the compound is 7.6 percent).

EXAMPLE l3 Illustrated in this example is the production of 0,0-diethylS-[ 2-chlorol 2-benzothiazolinone-3 -yl )ethyl] phosphorothioate.

By the procedure of Example 9, 14.9 w of 3-( 1,2-dichloroethyl)-2-benzothiazolinone and 12.4 w of ammonium 0,0-diethylphosphorothioate are reacted in 100 v of acetonitrile and the desiredproduct is isolated. It typically is an oil (18.6 w) consistingessentially of 0,0-diethyl S-[2- 29;!;Qf; miqth z y thy phosphorothioateand ahal yzes 8.3 percent phosphorous (the theoretical value forphosphorous in the compound is 7.9 percent).

Typical results obtained in employing the compounds of this invention assouthern army worm toxicants are illustrated by the following actualtest data which include test data obtained on known comparablecompounds.

The test procedure employed to obtain these data is as follows.

An emulsifiable concentration made by dissolving in toluene (3 parts byweight) a sample (3 parts by weight) of the material to be tested, andadding 3 parts by weight of polyoxyethylene (20) sorbitan monolaurate(an emulsifier in which the oxyethylene content is about 20 molpercent). The concentrate is then admixed with sufficient water to forman aqueous dispersion containing the test material at a designatedconcentration based on the weight of the dispersion.

Using standard spraying equipment under standard conditions, the aqueousdispersion is sprayed on fresh lima bean leaves (Woods Prolific) about 3inches long, each held by its stem in a vial containing water. Each leafis sprayed on the upper surface for ten seconds and then allowed to dry.Each leaf is then placed in a small plastic box (43 cubic inches volume)with 10 third and fourth instar southern army worm larvae (Prodeniaeridania), and the box is stored for 48 hours at 7880 F. The larvae arethen inspected and the percentage of dead or moribund larvae determined.

The test data obtained by the foregoing procedure are summarized in thefollowing table. The samples tested consisted essentially of theindicated compounds at substantially the same degree of purity (80-99percent).

Percent kill at 0.1 wt. 0.05 wt. 0.025 Wt. percent percent percent cone.cone. cone.

Compound a 11 0,0-dimethyl S-[2-brom0-1- (2'-benzothinzolinone-3'-yl)-ethyl] phos horodithioate. 12 0,0-dimethy S-[2-chlor0-1-(2-benz0thiazolinone-3'-yl)- ethyl] phos horodithioate. 13 0,0-dimothyS-(2-benz0thinzolinone-S-ylhnethyl phosphorodlthionte. 0,0-rliothylS-[2-hr0m0-l- (2'-honzothinzollnone-3- yl)thyl] phosphorodlthion 160,0-diethyl S-(Z-benzothia- 0 0 0 z0linone-3-yl)methylphosphorodithioate. 17 0,0-diethyl S-[2-chl0r0-1-(2'-benz0thiazolinone-3- yl)ethyl] phosphorothioate.

H. 4 100 JO 80 From the foregoing data it can be seen that the compoundsof this invention (Test samples l-4, 6, 7, 9-12, 14 15 and 17) arehighly toxic to southern army worm larvae with the diethyl compoundsbeing generally substantially more toxic to the larvae than thecorresponding dimethyl compounds (compare Test Sample 3 data with TestSample 1 data, Test Sample 4 data with Test Sample 2 data, Test Sample14 data with Test Sample 1 1 data, and Test Sample 15 data with TestSample 12 data), and the 2-benzoxazolinone derivatives being generallysubstantially more toxic than the corresponding 2- benzothiazolinonederivatives (compare Test Sample 2 data with Test Sample 11 data, TestSample 3 data with Test Sample 15 data, Test Sample 4 data with TestSample 14 data, and Test Sample 9 data with Test Sample 17 data).Moreover, it can be observed that the compounds of this inventiongenerally are substantially more toxic to southern army worm larvae thanthe comparable compounds (Test Samples 5, 8, l3 and 16) of the prior art(compare the data of Test Samples 3 and 4 with the data of Test Sample5, the data of Test Samples 6 and 7 with the data of Test Sample 8, thedata of Test Samples 1 l and 12 with the data of Test Sample 13, and thedata of Test Samples 14 and 15 with the data of Test Sample 16).

Hence, this invention provides new and useful compounds andcompositions.

Other advantages, features and specific embodiments of this inventionwill become readily apparent to those exercising ordinary skill in theart after reading the foregoing disclosures.

These specific embodiments are within the scope of the claimed subjectmatter unless expressly excluded by claim language. Also, while specificembodiments of this invention have been described in considerabledetail, variations and modifications of them can be efiected withoutdeparting from the spirit and scope of the invention as disclosed andclaimed.

The term consisting essentially of as used in this specifcation excludesany unrecited substance at a concentration sufficient to substantiallyadversely affect the essential properties and characteristics of therecited substance or substances. while permitting the presence of one ormore unrecited substances at concentrations insufficient tosubstantially adversely affect said essential properties andcharacteristics.

What I claim and desire to protect by Letters Patent is:

wherein each R is lower alkyl, Y is selected from the group consistingof 0x0 and thioxo, X is halo, A is selected from the group consisting ofoxy and thio, and each R is selected from the group consisting ofhydrogen and halo.

2. A compound according to claim 1, wherein Y is thioxo and A is oxy.

3. A compound according to claim 2, wherein X is bromo and each R ishydrogen.

4. A compound according to claim 3, wherein each R is methyl.

5. A compound according to claim 3, wherein each R is ethyl.

6. A compound according to claim 2, wherein X is chloro and each R ishydrogen.

7. A compound according to claim 6, wherein R is methyl.

8. A compound according to claim 6, wherein R is ethyl.

9. A compound according to claim 2, wherein X is chloro, and the R atthe 6 position is chloro.

10. A compound according to claim 9, wherein the remaining Rs arehydrogen, and each R is ethyl.

1 l. A compound according to claim 9, wherein the R at the 5 position ischloro, the remaining R's are hydrogen, and each R is ethyl.

12. A compound according to claim 1, wherein Y is 0x0 and A is oxy.

13. A compound according to claim 12, wherein X is chloro, each R ishydrogen and each R is ethyl.

14. A compound according to claim 12, wherein X is chloro, R at the 6'position is chloro, the remaining R's are hydrogen, and each R is ethyl.

15. A compound according to claim 1, wherein Y is thio and A is thioxo.

16. A compound according to claim 15, wherein X is bromo and each R ishydrogen.

17. A compound according to claim 16, wherein each R is methyl.

18. A compound according to claim 16, wherein each R is ethyl.

19. A compound according to claim 15, wherein Y is chloro and each R ishydrogen.

20. A compound according to claim 19, wherein each R is methyl.

21. A compound according to claim 19, wherein each R is ethyl.

22. A compound according to claim 1, wherein Y is 0x0 and A is thioxo.

23. A compound according to claim 22, wherein X is chloro, each R ishydrogen and each R is ethyl.

2. A compound according to claim 1, wherein Y is thioxo and A is oxy. 3.A compound according to claim 2, wherein X is bromo and each R'' ishydrogen.
 4. A compound according to claim 3, wherein each R is methyl.5. A compound according to claim 3, wherein each R is ethyl.
 6. Acompound according to claim 2, wherein X is chloro and each R'' ishydrogen.
 7. A compound according to claim 6, wherein R is methyl.
 8. Acompound according to claim 6, wherein R is ethyl.
 9. A compoundaccording to claim 2, wherein X is chloro, and the R'' at the 6''position is chloro.
 10. A compound according to claim 9, wherein theremaining R''s are hydrogen, and each R is ethyl.
 11. A compoundaccording to claim 9, wherein the R'' at the 5'' position is chloro, theremaining R''s are hydrogen, and each R is ethyl.
 12. A compoundaccording to claim 1, wherein Y is oxo and A is oxy.
 13. A compoundaccording to claim 12, wherein X is chloro, each R'' is hydrogen andeach R is ethyl.
 14. A compound according to claim 12, wherein X ischloro, R'' at the 6'' position is chloro, the remaining R''s arehydrogen, and each R is ethyl.
 15. A compound according to claim 1,wherein Y is thio and A is thioxo.
 16. A compound according to claim 15,wherein X is bromo and each R'' is hydrogen.
 17. A compound according toclaim 16, wherein each R is methyl.
 18. A compound according to claim16, wherein each R is ethyl.
 19. A compound according to claim 15,wherein Y is chloro and each R'' is hydrogen.
 20. A compound accordingto claim 19, wherein each R is methyl.
 21. A compound according to claim19, wherein each R is ethyl.
 22. A compound according to claim 1,wherein Y is oxo and A is thioxo.
 23. A compound according to claim 22,wherein X is chloro, each R'' is hydrogen and each R is ethyl.